CN102597026B - 用于聚二烯烃生产的方法和催化剂体系 - Google Patents

用于聚二烯烃生产的方法和催化剂体系 Download PDF

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Publication number
CN102597026B
CN102597026B CN201080048068.7A CN201080048068A CN102597026B CN 102597026 B CN102597026 B CN 102597026B CN 201080048068 A CN201080048068 A CN 201080048068A CN 102597026 B CN102597026 B CN 102597026B
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vinyl
silane
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allyl
allyl group
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CN102597026A (zh
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史蒂文·骆
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Bridgestone Corp
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Bridgestone Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/54Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
    • C08F4/545Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof rare earths being present, e.g. triethylaluminium + neodymium octanoate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06Butadiene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/06Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/602Component covered by group C08F4/60 with an organo-aluminium compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/61Pretreating the metal or compound covered by group C08F4/60 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/612Pretreating with metals or metal-containing compounds
    • C08F4/616Pretreating with metals or metal-containing compounds with silicon or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F36/06Butadiene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/52Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/58Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with silicon, germanium, tin, lead, antimony, bismuth or compounds thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerization Catalysts (AREA)
CN201080048068.7A 2009-08-24 2010-08-24 用于聚二烯烃生产的方法和催化剂体系 Expired - Fee Related CN102597026B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US23616809P 2009-08-24 2009-08-24
US61/236,168 2009-08-24
PCT/US2010/046482 WO2011028523A2 (en) 2009-08-24 2010-08-24 Process and catalyst system for polydiene production

Publications (2)

Publication Number Publication Date
CN102597026A CN102597026A (zh) 2012-07-18
CN102597026B true CN102597026B (zh) 2014-11-26

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Country Link
US (1) US8765887B2 (ja)
EP (1) EP2470574B1 (ja)
JP (1) JP5791607B2 (ja)
KR (1) KR101685232B1 (ja)
CN (1) CN102597026B (ja)
BR (1) BR112012004109B1 (ja)
CZ (1) CZ306310B6 (ja)
RU (2) RU2539596C2 (ja)
WO (1) WO2011028523A2 (ja)
ZA (1) ZA201201302B (ja)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112013019813B1 (pt) * 2011-02-05 2021-11-16 Bridgestone Corporation Catalisador de complexo de lantanídeo e método de polimerização aplicando o mesmo
US9260593B2 (en) * 2011-12-13 2016-02-16 Tsrc Corporation Conjugated diene rubber modified with polar alkoxysilane, method and composition thereof
WO2013115242A1 (ja) * 2012-01-31 2013-08-08 旭化成ケミカルズ株式会社 共役ジエン系モノマーの重合触媒組成物
EP2825574B1 (en) * 2012-03-14 2016-02-24 Bridgestone Corporation Process for producing polydienes
JP6157806B2 (ja) * 2012-05-15 2017-07-05 住友化学株式会社 共役ジエン系重合体変性物及び重合体組成物
SG11201603025RA (en) * 2013-10-18 2016-05-30 Trinseo Europe Gmbh Vinylsilanes for use in functionalized elastomeric polymers
JP6287519B2 (ja) * 2014-04-15 2018-03-07 Jsr株式会社 新規なケイ素化合物及び重合体
PL3059240T3 (pl) 2015-02-18 2020-03-31 Trinseo Europe Gmbh Wielowinyloaminosilany jako środki rozgałęziające dla funkcjonalizowanych polimerów elastomerowych
KR20170000756A (ko) * 2015-06-24 2017-01-03 주식회사 엘지화학 공액 디엔계 중합체 제조용 촉매 조성물 및 이를 이용하여 제조된 공액 디엔계 중합체
WO2016209043A1 (ko) * 2015-06-24 2016-12-29 주식회사 엘지화학 공액 디엔계 중합체 제조용 촉매 조성물 및 이를 이용하여 제조된 공액 디엔계 중합체
EP3363825B1 (en) 2015-10-12 2021-04-14 Institute Of Chemistry, Chinese Academy Of Sciences Use of organic siloxane, and polyolefin in-reactor alloy and preparation method thereof
JP6857177B2 (ja) * 2015-10-12 2021-04-14 中国科学院化学研究所Institute Of Chemistry, Chinese Academy Of Sciences オレフィン重合触媒及びその製造方法、オレフィン重合触媒システム及びその使用、並びにポリオレフィン樹脂の製造方法
US10934373B2 (en) 2015-10-12 2021-03-02 Institute Of Chemistry, Chinese Academy Of Sciences Use of organosilane, and polyolefin resin and preparation method thereof
ES2685917T3 (es) * 2015-10-21 2018-10-15 Trinseo Europe Gmbh Dienos funcionalizados con aminosilano para el uso en la funcionalización de polímeros elastoméricos
KR102019841B1 (ko) * 2015-12-22 2019-09-10 주식회사 엘지화학 변성 공액 디엔계 중합체의 제조방법 및 이에 의해 제조된 변성 공액 디엔계 중합체
US10059788B2 (en) 2016-04-29 2018-08-28 Exxonmobil Chemical Patents Inc. Organoaluminum activators on clays
ES2717151T3 (es) 2016-06-17 2019-06-19 Trinseo Europe Gmbh Potenciamiento mediado por silano de la estabilidad de almacenamiento de caucho
US11059920B2 (en) * 2016-07-29 2021-07-13 Bridgestone Corporation Process for producing high cis-1,4-polydiene with lanthanide-based catalyst compositions
WO2018045291A1 (en) * 2016-09-02 2018-03-08 Bridgestone Corporation Production of cis-1,4-polydienes with multiple silane functional groups prepared by in-situ hydrosilylation of polymer cement
KR101825613B1 (ko) * 2016-09-19 2018-02-05 한화토탈 주식회사 저취기 특성을 나타내는 플라스틱 병뚜껑용 폴리에틸렌 수지 조성물의 제조방법 및 이로부터 제조된 성형품
KR102187173B1 (ko) * 2016-12-23 2020-12-07 주식회사 엘지화학 고무 조성물 및 이의 제조방법
CN109320638B (zh) * 2018-09-29 2021-03-26 四川锦成化学催化剂有限公司 乙烯聚合用Ziegler-Natta催化剂组分和催化剂
US10947380B2 (en) 2018-12-20 2021-03-16 The Goodyear Tire & Rubber Company Functionalized polymer, rubber composition and pneumatic tire
US11767388B1 (en) 2019-09-18 2023-09-26 The Goodyear Tire & Rubber Company Silicon-functionalized rubber

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6130299A (en) * 1996-12-04 2000-10-10 Jsr Corporation Method for preparing conjugated diene polymer
US6492476B1 (en) * 1999-10-28 2002-12-10 Bayer Aktiengesellschaft Catalyst based on rare earth metal compounds

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL124889C (ja) * 1963-03-01
DE2039017A1 (de) * 1969-08-13 1971-04-01 Inst Neftechimicheskogo Sintez Dilithiumorganische Katalysatoren zur Polymerisation von Dien- und Vinylmonomeren und Polymerisationsverfahren
GB1480519A (en) * 1974-10-10 1977-07-20 Inst Neftekhimsinteza Im Av To Silicon containing carbochain copolymers
SU1840584A1 (ru) * 1977-06-01 2007-08-20 Открытое акционерное общество "СК ПРЕМЬЕР" Способ получения низкомолекулярных каучуков
DE69722925T2 (de) * 1996-04-17 2004-05-19 Nippon Zeon Co., Ltd. Kautschukzusammensetzung
US5747404A (en) * 1996-05-28 1998-05-05 Lyondell Petrochemical Company Polysiloxane supported metallocene catalysts
TW541318B (en) * 2000-07-04 2003-07-11 Mitsui Chemicals Inc Process for producing polar olefin copolymer and polar olefin copolymer obtained thereby
NO20013880L (no) * 2000-08-22 2002-02-25 Rohm & Haas Matriks og fremgangsmåte for fremstilling av polyolefiner
DE60226270T2 (de) * 2001-12-07 2009-07-16 Société de Technologie Michelin Verfahren zur herstellung von butadien/isopren-copolymeren und dabei erhaltene copolymere
EP1544218A1 (en) * 2003-12-19 2005-06-22 Borealis Technology Oy Process for producing olefin polymers
CN100554285C (zh) * 2005-04-15 2009-10-28 株式会社普利司通 改性共轭二烯系共聚物、橡胶组合物及轮胎
US8088868B2 (en) 2006-12-19 2012-01-03 Bridgestone Corporation Polymers functionalized with protected oxime compounds
ZA200711158B (en) * 2006-12-28 2009-03-25 Bridgestone Corp A method for producing functionalized cis-1,4-polydienes having high cis-1,4-linkage content and high functionality

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6130299A (en) * 1996-12-04 2000-10-10 Jsr Corporation Method for preparing conjugated diene polymer
US6492476B1 (en) * 1999-10-28 2002-12-10 Bayer Aktiengesellschaft Catalyst based on rare earth metal compounds

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CZ2012126A3 (cs) 2012-07-04
ZA201201302B (en) 2012-10-31
RU2539596C2 (ru) 2015-01-20
KR101685232B1 (ko) 2016-12-09
US8765887B2 (en) 2014-07-01
RU2014147736A3 (ja) 2018-03-30
EP2470574B1 (en) 2014-09-17
JP5791607B2 (ja) 2015-10-07
US20120165484A1 (en) 2012-06-28
BR112012004109B1 (pt) 2019-08-13
JP2013502508A (ja) 2013-01-24
EP2470574A4 (en) 2013-07-31
CN102597026A (zh) 2012-07-18
EP2470574A2 (en) 2012-07-04
RU2012111258A (ru) 2013-10-10
RU2014147736A (ru) 2016-06-20
CZ306310B6 (cs) 2016-11-23
WO2011028523A2 (en) 2011-03-10
KR20120068885A (ko) 2012-06-27
RU2655029C2 (ru) 2018-05-25
BR112012004109A2 (pt) 2017-09-26
WO2011028523A3 (en) 2011-06-16

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